US5215569A - Substituted pyridines - Google Patents

Substituted pyridines Download PDF

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US5215569A
US5215569A US07/738,702 US73870291A US5215569A US 5215569 A US5215569 A US 5215569A US 73870291 A US73870291 A US 73870291A US 5215569 A US5215569 A US 5215569A
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carbonyl
alkoxy
alkyl
methyl
amino
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Mark W. Drewes
Peter Muller
Hans-Joachim Santel
Klaus Lurssen
Robert R. Schmidt
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Bayer AG
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Bayer AG
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Assigned to BAYER AKTIENGESELLSCHAFT reassignment BAYER AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: LURSSEN, KLAUS, DREWES, MARK W., MULLER, PETER, SCHMIDT, ROBERT R., SANTEL, HANS-JOACHIM
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms

Definitions

  • the invention relates to new substituted pyridines, to processes and to new intermediates for their preparation, and to their use as herbicides.
  • Q represents oxygen or sulphur
  • R 1 and R 2 are identical or different and represent hydrogen, halogen, alkyl, halogenoalkyl, alkoxyalkyl, alkoxy, halogenoalkoxy, alkylthio, alkylamino or dialkylamino,
  • R 3 represents hydrogen, amino, nitro, hydroxyl, halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylamino, dialkylamino, alkylcarbonylamino, alkoxycarbonylamino or alkylsulphonylamino,
  • R 4 represents hydrogen or alkyl
  • Z represents oxygen or one of the groups below: ##STR4## where R 5 represents hydrogen, hydroxyl or amino, or represents in each case optionally substituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkoxycarbonylalkoxy, alkylamino, dialkylamino, alkylcarbonylamino, alkoxycarbonylamino, alkylsulphonylamino, aryl, aralkyl, aryloxy, aralkyloxy, arylamino, aralkylamino, N-alkyl-N-arylamino, hetarylamino, hetarylcarbonylamino, arylcarbonylamino or arylsulphonylamino,
  • R 6 represents hydrogen, halogen, cyano, carboxyl, alkoxycarbonyl, alkylcarbonylamino or dialkoxyphosphoryl and
  • R 7 represents formyl, cyano, carboxyl, hydroxymethyl or carbamoyl, or represents in each case optionally substituted alkoxycarbonyl, cycloalkoxycarbonyl, alkylthiocarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl, dialkylaminocarbonyl, alkylaminocarbonylalkoxycarbonyl, dialkylaminocarbonylalkoxycarbonyl, arylaminocarbonylalkoxycarbonyl, N-alkyl-N-arylaminocarbonylalkoxycarbonyl, pyrrolidinylcarbonyl, piperidinylcarbonyl, morpholinylcarbonyl, piperazinylcarbonyl, aryloxycarbonyl, aralkyloxycarbonyl, heterocyclylalkoxycarbonyl, arylthiocarbonyl, aralkylthiocarbonyl, arylaminocarbonyl,
  • hydroxyalkylpyridines of the general formula (II) ##STR5## in which A, Q, R 1 , R 2 , R 3 and R 4 have the abovementioned meaning, are reacted with oxidants ("dehydration agents"), if appropriate in the presence of diluents, or when
  • Z represents the group N-R 5 or the group ##STR6## and A, Q, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 have the abovementioned meaning,
  • the new substituted pyridines of the general formula (I) are distinguished by a powerful herbicidal activity.
  • alkyl on its own or in composite radicals such as, for example, alkylamino or alkoxycarbonylalkyl
  • alkyl represents alkyl having preferably 1 to 6, particularly preferably 1 to 4 and especially 1 to 2 carbon atoms.
  • the following may preferably be mentioned by way of example: methyl, ethyl, n- and iso-propyl, and n-, i-, s- and tert.-butyl.
  • alkoxy and alkylthio on their own or in composite radicals such as, for example, alkoxycarbonyl or alkylthiocarbon-ylalkyl, represent alkoxy, or alkylthio, having preferably 1 to 6, particularly preferably 1 to 4, and especially preferably 1 to 2 carbon atoms.
  • the following may preferably be mentioned by way of example: methoxy, ethoxy, n- and i-propoxy, n-, i-, s- and tert.-butoxy, methylthio, ethylthio, n- and i-propylthio, n-, i-, s- and tert.-butylthio.
  • alkenyl and alkinyl on their own or in composite radicals represent alkenyl, or alkinyl, having preferably 3 to 6, particularly preferably 3 or 4, carbon atoms.
  • the following may preferably be mentioned by way of example: allyl and propargyl.
  • halogenoalkyl, halogenoalkoxy and halogenoalkylthio represent in each case straight-chain or branched halogenoalkyl, halogenoalkoxy or halogenoalkylthio having 1 to 4, and preferably 1 or 2, carbon atoms and in each case 1 to 9 and preferably 1 to 5, identical or different halogen atoms as defined under halogen; the following may preferably be mentioned by way of example: fluoromethyl, chloromethyl, bromomethyl, fluoroethyl, chloroethyl, bromoethyl, fluoro-n.-propyl, chloro-n-propyl, dichloromethyl, difluoroethyl, trifluoroethyl, trichloroethyl, trifluorochloroethyl, chlorobutyl, fluorobutyl and, especially, difluoromethyl, trifluoromethyl, trichlor
  • the invention preferably relates to compounds of the formula (I) in which
  • A represents nitrogen or a C-X group, where X represents hydrogen or halogen
  • Q represents oxygen or sulphur
  • R 1 and R 2 are identical or different and represent hydrogen, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 2 -alkoxy-C 1 -C 2 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -halogenoalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylamino or di-(C 1 -C 2 -alkyl)-amino,
  • R 3 represents hydrogen, amino, nitro, hydroxyl, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -halogenoalkoxy, C 1 -C 4 -alkylamino, di-(C 1 -C 2 -alkyl)-amino, C 1 -C 4 -alkyl-carbonylamino, C 1 -C 4 -alkoxy-carbonylamino or C 1 -C 4 -alkylsulphonylamino,
  • R 4 represents hydrogen or C 1 -C 4 -alkyl
  • Z represents oxygen or one of the groups below: N-R 5 or ##STR8## where R 5 represents hydrogen, hydroxyl or amino, or represents in each case optionally halogen-substituted C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkinyl, C 1 -C 6 -alkoxy, C 3 -C 6 -alkenyloxy, C 1 -C 4 -alkoxy-carbonyl-C 1 -C 2 -alkoxy, C 1 -C 6 -alkyl-amino, di-(C 1 -C 2 -alkyl)-amino, C 1 -C 6 -alkyl-carbonylamino, C 1 -C 6 -alkoxy-carbonylamino, C 1 -C 6 -alkyl-sulphonylamino, or represents phenyl, phenyl-C 1 -C 4 -alky
  • R 6 represents hydrogen, halogen, cyano, carboxyl, C 1 -C 6 -alkoxy-carbonyl, C 1 -C 6 -alkylcarbonylamino or di-(C 1 -C 4 -alkoxy)-phosphoryl and
  • R 7 represents formyl, cyano, carboxyl, hydroxymethyl or carbamoyl, or represents C 1 -C 6 -alkoxy-carbonyl, C 5 -C 6 -cycloalkyloxy-carbonyl, C 1 -C 6 -alkylthio-carbonyl, C 1 -C 6 -alkylamino-carbonyl or C 5 -C 6 -cycloalkylamino-carbonyl, each of which is optionally substituted by halogen, carboxyl or C 1 -C 4 -alkoxy-carbonyl, or represents di-(C 1 -C 2 -alkyl)-amino-carbonyl, or represents C 1 -C 4 -alkylamino-carbonyl-C 1 -C 4 -alkoxy-carbonyl, or represents di-(C 1 -C 2 -alkyl)-amino-carbonyl, or represents C 1 -C 4 -alkylamino
  • aliphatic hydrocarbon radicals for example alkyl, alkenyl, alkinyl
  • hetero atoms for example in alkoxy, alkylthio or alkylamino
  • compositions such as, for example, halogenoalkyl or halogenoalkoxy, which are mentioned in the definition of the compounds according to the invention, are in each case straight-chain or branched.
  • Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, especially fluorine or chlorine
  • the invention especially relates to compounds of the formula (I) in which
  • A represents nitrogen or a CH group
  • R 1 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxymethyl, methoxy, ethoxy, difluoromethoxy, methylthio, methylamino, ethylamino or dimethylamino,
  • R 2 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, methylamino, ethylamino or dimethylamino,
  • R 3 represents hydrogen, amino, hydroxyl, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, methylamino, dimethylamino, acetylamino, methoxycarbonylamino, or methylsulphonylamino,
  • R 4 represents hydrogen or methyl
  • Z represents oxygen or one of the groups below: ##STR9## where R 5 represents hydrogen, hydroxyl or amino, or represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, allyl, propargyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, allyloxy, methoxycarbonylmethoxy, ethoxycarbonylmethoxy, methoxycarbonylethoxy, ethoxycarbonylethoxy, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec-butylamino, tert-butylamino, dimethylamino, acetylamino, propionylamino
  • R 6 represents hydrogen, fluorine, chlorine, cyano, carboxyl, C 1 -C 4 -alkoxy-carbonyl, C 1 -C 4 -alkylcarbonylamino, dimethoxyphosphoryl or diethoxyphosphoryl, and
  • R 7 represents formyl, cyano, carboxyl, hydroxymethyl or carbamoyl, or represents C 1 -C 4 -alkoxy-carbonyl, C 5 -C 6 -cycloalkyloxy-carbonyl, C 1 -C 4 -alkylthiocarbonyl, C 1 -C 4 -alkylamino-carbonyl or C 5 -C 6 -cycloalkylamino-carbonyl, each of which is optionally substituted by fluorine, chlorine, carboxyl or C 1 -C 4 -alkoxy-carbonyl, or represents dimethylaminocarbonyl, or represents C 1 -C 4 -alkylaminocarbonyl-C 1 -C 4 -alkoxy-carbonyl, or represents dimethylaminocarbonyl-C 1 -C 4 -alkoxy-carbonyl, or represents dimethylaminocarbonyl-C 1 -C 4 -alkoxy-carbonyl, or represents
  • Particularly preferred groups of compounds of the formula (I) are those of the formulae (IA) and (IB) below in which A, Q, R 1 , R 2 , R 3 , R 4 and Z in each case have the meanings given above as being especially preferred.
  • the group (IA) may be especially emphasised.
  • Very particularly preferred compounds of the formula (I), in particular of the formulae (IA) and (IB), are those in which
  • A represents a CH group
  • R 1 represents methoxy
  • R 2 represents methoxy
  • R 3 represents hydrogen or fluorine
  • R 4 represents hydrogen
  • R 5 must be particularly emphasised: Hydrogen, hydroxyl, amino, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert.-butyl, methylamino, ethylamino, n-propylamino, i-propylamino, n-butylamino, i-butylamino, sec-butylamino, tert.-butylamino, dimethylamino, acetylamino, propionylamino, methoxycarbonylamino or ethoxycarbonylamino, or phenyl, benzyl, phenylamino, benzylamino, or N-methyl-N-phenylamino, each of which is monosubstituted to trisubstituted by identical or different substituents from the series comprising fluorine,
  • R 6 Hydrogen, cyano, carboxyl and C 1 -C 4 -alkoxy-carbonyl.
  • R must be particularly emphasised: Cyano, carboxyl and C 1 -C 4 -alkoxy-carbonyl.
  • A, Q, R 1 , R 2 , R 3 and R 4 preferably, or especially, have those meanings which have already been indicated above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or especially preferred, for A, Q, R 1 , R 2 , R 3 and R 4 .
  • Examples of the starting substances of the formula (II) which may be mentioned are: 3-(4,6-dimethyl-pyrimidin-2-yl-oxy)-, 3-(4-methoxy-6-methyl-pyrimidin-2-yl-oxy)-, 3-(4,6-dimethoxy-pyrimidin-2-yl-oxy)-, 3-(4-methoxy-6-trifluoromethyl-pyrimidin-2-yl-oxy)-, 3-(4,6-dimethyl-s-triazin-2-yl-oxy)-, 3-(4-methoxy-6-methyl-s-triazin-2-yl-oxy)- and 3-(4,6-dimethoxy-s-triazin-2-yl-oxy)-2-hydroxymethyl-pyridine.
  • R 4 has the abovementioned meaning
  • M represents a metallic or metal-containing component which is customary in the case of (optionally complex) metal hydrides or organometal compounds,
  • a diluent such as, for example, diethyl ether, dimethoxyethane, tetrahydrofuran, methanol, ethanol or isopropanol, at temperatures between -70° C. and +50° C., and the product is worked up by customary methods (cf. preparation examples).
  • A, Q, R 1 , R 2 and R 3 preferably, or especially, have those meanings which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or especially preferred, for A, Q, R 1 , R 2 and R 3 , and Y preferably represents chlorine, hydroxyl, methoxy or ethoxy.
  • Examples of the starting substances of the formula (IV) which may be mentioned are: 3-(4,6-dimethyl-pyrimidin-2-yl-oxy)-, 3-(4-methoxy-6 -methyl-pyrimidin-2-yl-oxy)-, 3-(4,6-dimethoxy-pyrimidin-2-yl-oxy)-, 3-(4-methoxy-6-trifluoromethyl-pyrimidin-2-yl-oxy)-, 3-(4,6-dimethyl-s-triazin-2-yl-oxy)-, 3-(4-methoxy-6-methyl-s-triazin-2-yl-oxy)- and 3-(4,6-dimethoxy-s-triazin-2-yl-oxy)-pyridin-2-carboxylicacid and the corresponding carboxylic acid chlorides, the methyl esters and the ethyl esters.
  • the pyridine carboxylic acid derivatives of the formula (IV) are known and/or can be prepared by processes known per se (cf. EP-A 249,707).
  • R 4 preferably, or especially, has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or especially preferred, for R 4 , and M preferably represents a metal from the series comprising lithium, sodium, potassium, magnesium, calcium, boron and aluminium, to which, if appropriate (if polyvalent), hydrogen atoms, alkali metal atoms or halogen atoms are bonded additionally.
  • Examples of the compounds of the formula (V) which may be mentioned are: lithium hydride, sodium hydride, potassium hydride, magnesium hydride and calcium hydride, lithium tetrahydridoborate, sodium tetrahydridoborate and potassium tetrahydridoborate ("borohydride", “boranate”), lithium tetrahydridoaluminate, sodium tetrahydridoaluminate and potassium tetrahydridoaluminate (“alanate”), methyllithium, butyllithium, methylmagnesium chloride, methylmagnesium bromide and methylmagnesium iodide, ethylmagnesium chloride-bromide, propylmagnesium chloridebromide and isopropylmagnesium chloride-bromide and ethylmagnesium iodide, propylmagnesium iodide and isopropylmagnesium iodide
  • the compounds of the formula (V) are known chemicals for synthesis.
  • Oxidants which are preferably employed for this purpose are substances which are customarily used for dehydrating alcohols to give aldehydes or ketones such as, for example, manganese(IV) oxide (“manganese dioxide”), dimethyl sulphoxide/oxalyl chloride (Swern's reagent), chromium(VI) oxide or sodium dichromate/sulphuric acid.
  • Process (a) according to the invention for the preparation of the new substituted pyridines of the formula (I) is preferably carried out using diluents.
  • Diluents which are suitable for this purpose are virtually all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropy
  • reaction temperatures can be varied within a substantial range.
  • the process is carried out at temperatures between -80° C. and +150° C., preferably at temperatures between -60° C. and +100° C.
  • process (a) according to the invention is carried out under atmospheric pressure. However, it is also possible to carry out the process under increased or reduced pressure.
  • the starting compound of the formula (II) is first introduced into a suitable diluent and the oxidant is slowly added to this mixture.
  • the reaction mixture is stirred at the temperature required until the reaction is complete and worked up in the customary manner (cf. preparation examples).
  • Formula (Ia) provides a general definition of the substituted pyridines to be used as starting substances in process (b) according to the invention for the preparation of compounds of the formula (I).
  • A, Q, R 1 , R 2 , R 3 and R 4 preferably, or especially, have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or especially preferred, for A, Q, R 1 , R 2 , R 3 and R 4 .
  • substituted pyridines of the formula (Ia) are new compounds according to the invention; they can be prepared by process (a) according to the invention.
  • Formula (III) provides a general definition of the amino or methylene compounds furthermore to be used as starting substances in process (b) according to the invention for the preparation of compounds of the formula (I).
  • Z preferably, or especially, has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or especially preferred, for Z, with the exception of oxygen.
  • the starting substances of the formula (III) which may be mentioned are: ammonia, hydroxylamine, hydrazine, methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, tert-butylamine, allylamine, propargylamine, O-methyl-, O-ethyl-, O-propyl-, O-isopropyl-, O-butyl-, O-isobutyl- and O-sec-butyl-hydroxylamine, O-allyl-hydroxylamine, methyl aminooxyacetate and ethyl aminooxyacetate, methyl ⁇ -aminooxypropionate and ethyl ⁇ -a
  • the starting substances of the formula (III) are known chemicals for synthesis.
  • Process (b) according to the invention for the preparation of the new substituted pyridines of the formula (I) is preferably carried out using diluents.
  • Diluents which are suitable for this purpose are, besides water, virtually all inert organic solvents.
  • aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as, for example, acetonitrile and propionitrile, amides such as
  • reaction auxiliaries are substances which are customarily used for controlling and/or accelerating condensation reactions between carbonyl compounds and amino or methylene compounds. They especially include nitrogen compounds such as, for example, ammonium acetate, ⁇ -alanine, pyridine and piperidine.
  • reaction temperatures can be varied within a substantial range.
  • the process is carried out at temperatures between 0° C. and 150° C., preferably at temperatures between 10° C. and 120° C.
  • Process (b) according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process under increased or reduced pressure.
  • the starting substances required in each case are generally employed in approximately equimolar amounts. However, it is also possible to use one of the two components employed in each case in a larger excess.
  • the reactions are carried out in a suitable diluent, if appropriate in the presence of a reaction auxiliary, and the reaction mixture is stirred for several hours at the particular temperature required.
  • Working-up in the process according to the invention is carried out in each case by customary methods (compare the preparation examples).
  • the active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers.
  • weeds in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
  • the active compounds according to the invention can be used, for example, in connection with the following plants:
  • the compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on lawns, turf and pasture-land, and for the selective combating of weeds in annual cultures.
  • the compounds of the formula (I) according to the invention are especially suitable for selectively combating monocotyledon and dicotyledon weeds by the pre-emergence and the post-emergence method.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
  • formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foam-forming agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • liquid solvents there are suitable in the main: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water.
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • solid carriers for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsul
  • Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
  • colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs
  • trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • the formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
  • Suitable herbicides for the mixtures are known herbicides, such as, for example, 1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione (AMETHYDIONE) or N-(2-benzothiazolyl-)-N,N'-dimethylurea (METABENZTHIAZURON) for combating weeds in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) for combating weeds in sugar beet and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one (METRIBUZIN) for combating weeds in sugar beet and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin
  • the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
  • the active compounds according to the invention can be applied either before or after emergence of the plants.
  • the amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.01 and 10 kg of active compound per hectare of soil surface, preferably between 0.05 and 5 kg per ha.
  • a mixture of 18.3 g (0.06 mol) of ethyl 3-(4,6-dimethoxypyrimidine-2-yl-oxy)-pyridin-2-carboxylate and 200 ml of ethanol is cooled to 0° C. to 5° C., and 6.5 g (0.17 mol) of sodium borohydride are added in portions, with stirring.
  • a solution of 10 g of calcium chloride in 60 ml of ethanol is then added dropwise, and the mixture is stirred for 1 hour at 0° C. to 5° C.
  • the mixture is subsequently acidified using hydrochloric acid and then again rendered weakly alkaline by adding sodium carbonate.
  • the mixture is extracted using diethyl ether, the extraction solution is concentrated, the residue is brought to crystallisation by trituration with diethyl ether/petroleum ether, and the product is isolated by filtration with suction.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of the active compound. It is expedient in this case to keep constant the amount of water per unit area.
  • the concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive.
  • the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • Test plants which have a height of 5-15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound desired per unit area.
  • the concentration of the spray liquor is so chosen that the particular amounts of active compound desired are applied in 1000 l of water/ha.
  • the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US07/738,702 1990-08-10 1991-07-31 Substituted pyridines Expired - Fee Related US5215569A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4025338 1990-08-10
DE4025338A DE4025338A1 (de) 1990-08-10 1990-08-10 Substituierte pyridine

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US (1) US5215569A (ja)
EP (1) EP0472925B1 (ja)
JP (1) JPH04305577A (ja)
BR (1) BR9103423A (ja)
CA (1) CA2048542A1 (ja)
DE (2) DE4025338A1 (ja)
ES (1) ES2057679T3 (ja)
MX (1) MX9100415A (ja)
ZA (1) ZA916296B (ja)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5385880A (en) * 1991-03-26 1995-01-31 Kumiai Chemical Industry Co., Ltd. Pyridine derivative herbicidal composition containing the same, and method for killing weeds
US5561101A (en) * 1990-06-07 1996-10-01 Sandoz Ltd. Substituted phthalides and heterocyclic phthalides
CN1044369C (zh) * 1992-04-23 1999-07-28 组合化学工业株式会社 吡啶甲酸及除草组合物
WO2001025220A1 (en) * 1999-10-07 2001-04-12 Amgen Inc. Triazine kinase inhibitors
US6864255B2 (en) 2001-04-11 2005-03-08 Amgen Inc. Substituted triazinyl amide derivatives and methods of use
US6881737B2 (en) 2001-04-11 2005-04-19 Amgen Inc. Substituted triazinyl acrylamide derivatives and methods of use
WO2021080346A1 (ko) * 2019-10-24 2021-04-29 한국과학기술연구원 단백질 키나아제 저해 활성을 갖는 신규한 피리디닐트리아진 유도체 및 이를 포함하는 암의 예방, 개선 또는 치료용 약학 조성물

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5403816A (en) * 1990-10-25 1995-04-04 Kumiai Chemical Industry Co., Ltd. Picolinic acid derivative and herbicidal composition
US5380700A (en) * 1991-03-26 1995-01-10 Kumiai Chemical Industries Co., Ltd. Pyridine derivatives, herbicidal composition containing the same, and method for killing weeds
TR27713A (tr) * 1992-07-02 1995-06-22 Ihara Chemical Ind Co Piridin türevi, bunu hazirlamaya mahsus yöntem, bunu ihtiva eden herbisid terkibi, ve yabani otlari öldürmeye mahsus yöntem.
TR27733A (tr) * 1992-07-02 1995-06-28 Kumiai Chemical Industry Co Piridin tioeter türevi, bunu hazirlamaya mahsus yöntem, bunu ihtiva eden herbisid terkibi ve yabani otlari öldürmeye mahsus yöntem.
AU8033598A (en) * 1997-06-18 1999-01-04 Nissan Chemical Industries Ltd. Pyridine compounds and herbicides

Citations (5)

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Publication number Priority date Publication date Assignee Title
EP0242081A1 (en) * 1986-04-17 1987-10-21 Zeneca Limited Fungicides
EP0372329A2 (de) * 1988-12-09 1990-06-13 BASF Aktiengesellschaft Pyridinderivate und ihre Verwendung als herbizide Wirkstoffe
EP0374839A1 (en) * 1988-12-19 1990-06-27 MITSUI TOATSU CHEMICALS, Inc. 2-(4,6-Dimethoxy-2-pyrimidinyloxy)benzaldoximes, preparation processes thereof, herbicides containing the same, and herbicidal compositions containing the same along with other active ingredients
EP0402751A1 (de) * 1989-06-14 1990-12-19 BASF Aktiengesellschaft Salicylaldehyd- und Salicylsäurederivate sowie deren Schwefelanaloge, Verfahren zu ihrer Herstellung und ihre Verwendung als Herbizide und Bioregulatoren
US5015285A (en) * 1988-09-22 1991-05-14 Basf Aktiengesellschaft Aromatic carboxylic acid derivatives and the use thereof for controlling undesirable plant growth

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Publication number Priority date Publication date Assignee Title
US5129937A (en) * 1989-12-26 1992-07-14 Mitsui Toatsu Chemicals Incorporated Pyridyloxypyrimidine derivatives, preparation process thereof, and herbicidal compositions containing the same as active ingredients

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0242081A1 (en) * 1986-04-17 1987-10-21 Zeneca Limited Fungicides
US5015285A (en) * 1988-09-22 1991-05-14 Basf Aktiengesellschaft Aromatic carboxylic acid derivatives and the use thereof for controlling undesirable plant growth
EP0372329A2 (de) * 1988-12-09 1990-06-13 BASF Aktiengesellschaft Pyridinderivate und ihre Verwendung als herbizide Wirkstoffe
EP0374839A1 (en) * 1988-12-19 1990-06-27 MITSUI TOATSU CHEMICALS, Inc. 2-(4,6-Dimethoxy-2-pyrimidinyloxy)benzaldoximes, preparation processes thereof, herbicides containing the same, and herbicidal compositions containing the same along with other active ingredients
EP0402751A1 (de) * 1989-06-14 1990-12-19 BASF Aktiengesellschaft Salicylaldehyd- und Salicylsäurederivate sowie deren Schwefelanaloge, Verfahren zu ihrer Herstellung und ihre Verwendung als Herbizide und Bioregulatoren

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5561101A (en) * 1990-06-07 1996-10-01 Sandoz Ltd. Substituted phthalides and heterocyclic phthalides
US5385880A (en) * 1991-03-26 1995-01-31 Kumiai Chemical Industry Co., Ltd. Pyridine derivative herbicidal composition containing the same, and method for killing weeds
CN1044369C (zh) * 1992-04-23 1999-07-28 组合化学工业株式会社 吡啶甲酸及除草组合物
WO2001025220A1 (en) * 1999-10-07 2001-04-12 Amgen Inc. Triazine kinase inhibitors
US20040116388A1 (en) * 1999-10-07 2004-06-17 Amgen Inc. Kinase inhibitors
US7074789B2 (en) 1999-10-07 2006-07-11 Amgen Inc. Kinase inhibitors
US6864255B2 (en) 2001-04-11 2005-03-08 Amgen Inc. Substituted triazinyl amide derivatives and methods of use
US6881737B2 (en) 2001-04-11 2005-04-19 Amgen Inc. Substituted triazinyl acrylamide derivatives and methods of use
WO2021080346A1 (ko) * 2019-10-24 2021-04-29 한국과학기술연구원 단백질 키나아제 저해 활성을 갖는 신규한 피리디닐트리아진 유도체 및 이를 포함하는 암의 예방, 개선 또는 치료용 약학 조성물
US12466812B2 (en) 2019-10-24 2025-11-11 Korea Institute Of Science And Technology Pyridinyltriazine derivative having protein kinase inhibitory activity, and pharmaceutical composition for preventing, ameliorating, or treating cancer comprising same

Also Published As

Publication number Publication date
JPH04305577A (ja) 1992-10-28
BR9103423A (pt) 1992-05-19
ZA916296B (en) 1992-05-27
EP0472925B1 (de) 1994-08-31
DE4025338A1 (de) 1992-02-13
ES2057679T3 (es) 1994-10-16
MX9100415A (es) 1992-04-01
EP0472925A1 (de) 1992-03-04
DE59102729D1 (de) 1994-10-06
CA2048542A1 (en) 1992-02-11

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